Avrami法研究微量司盘85对棕榈油结晶动力学的影响

采用差示扫描量热仪（differential scanning calorimetry,DSC）分析棕榈油及其与司盘85混合物的等温结晶及熔融行为,通过Hoffman-Weeks法计算出样品的平衡熔点。采用Avrami方程进一步研究样品的等温结晶动力学,从而得到与结晶动力学相关的参数。结果表明：DSC分析显示司盘85可明显降低棕榈油的结晶率和成核速率。通过Hoffman-Weeks法和Avrami方程求得的温度数据具有良好的线性关系,表明Avrami方程适用于棕榈油结晶过程的研究,但在结晶后期出现偏离。拟合得到的Avrami指数（n）在2.37～2.77之间,可知样品二维和三维晶体生长同时存在;结晶速率（k）和半结晶时间（t1/2）随着添加剂的添加均变小。     

乳化剂对可可脂结晶行为的影响

从结晶热力学、动力学及形态学3个方面考察了5种乳化剂对可可脂结晶行为的影响。结果表明:单甘脂的添加降低了可可脂在25～30℃温度范围内的固体脂肪含量,不利于巧克力的加工。山梨醇酐单硬脂酸酯(Span60)的添加使可可脂晶体的三维球晶生长方式向二维平面晶体生长方式转变,并显著加快可可脂的结晶速率。Span60和聚乙氧基硬脂酸山梨糖醇(Tween60)缩短了可可脂的半结晶时间,而单甘脂、卵磷脂及聚甘油多聚蓖麻酸酯(PGPR)使可可脂的半结晶时间延长。偏光显微镜结果表明乳化剂的添加使得可可脂球晶的直径增大。     

湿面老化动力学研究

利用差示量热扫描仪测定在不同储藏温度条件下(-4、15、25、35℃)的湿面老化焓,应用Avrami模型描述淀粉在回生过程中的结晶行为,研究了贮存温度对湿面淀粉老化速率和淀粉结晶成核方式的影响。通过对模型线性回归后得到结晶速率常数k和Avrami指数n。结果表明,在本实验贮存温度区间内,湿面淀粉的老化结晶速率k随着贮存温度的升高而逐渐减小;在-4～15℃的贮存温度区间内,Avrami指数n均小于1,表明其结晶方式是瞬间成核,在25～35℃区间内,1相似文献   

Ultrasound assisted nucleation of some liquid and solid model foods during freezing

Power ultrasound has been proven to be useful in promoting the nucleation of ice in water-based solutions, and different mechanisms have been proposed to describe this phenomenon. In the present work, the use of ultrasound waves to induce dynamic nucleation in deionised water, sucrose solution, and agar gel samples was studied, and the mechanism of ultrasound assisted nucleation was discussed. The samples were frozen in an ethylene glycol–water mixture (− 20 °C) in an ultrasonic bath system after putting them into tubing vials. Ultrasound irradiation (25 kHz, 0.25 W cm⁻¹) was applied continuously for 1, 3, 5, 10 or 15 s at different sample's temperatures in the range of 0 °C to − 5 °C. The nucleation temperatures of the water, sucrose solution and agar gel samples without ultrasound irradiation, occurred stochastically at − 7.4 ± 2.4 °C, −10.6 ± 1.7 °C and − 7.5 ± 0.92 °C, respectively and followed normal distributions. Unlike agar gel samples, the nucleation temperatures of water and sucrose were induced by applying ultrasound for 5 s at different temperatures after a short delay, and linear relationships between the ultrasound irradiation temperatures and the nucleation temperatures were observed. Evaluation of the effect of different durations of ultrasound application on agar gels indicated that 1 s was not long enough to induce nucleation, 3 s was optimal, 5 s and 10 s produced heat and inhibited nucleation, and 15 s did not exhibit significant differences from 3 s and 10 s. It was concluded that longer irradiation durations (especially 5 s and 10 s) caused the sample to heat up, which interrupted or delayed the nucleation. Ultrasound irradiation for 3 s induced nucleation in agar gel samples at different temperatures resulting in a linear relationship between irradiation and nucleation temperatures. The observations indicated that the Hickling's theory, according to which vigorous collapses of bubbles are the only driving mechanism of nucleation, is not adequate to describe the ultrasound assisted nucleation. The results, however, were in agreement with results of some other researchers suggesting that secondary phenomena such as flow streams are also important for the initiation of nucleation. In conclusion, the use of ultrasound as a means to control the crystallisation process offers promising application in food freezing, though further investigations are needed for understanding the mechanisms, especially in solid foods.     

A kinetic analysis of crystallization of a milk fat model system

Crystallization behavior of milk fat, pure triacylglycerol (TAG) fraction of milk fat and three blends of 30, 40 and 50% of high-melting fraction (MDP=47.5°C) in low-melting fraction (MDP=16.5°C) of milk fat were studied by turbidimetry and nuclear magnetic resonance (NMR). Nucleation behavior was similar for these systems. In all cases, curves of log of induction time vs. temperature were continuous, which means that when samples were crystallized from the melt, only one polymorphic form was obtained at all temperatures. X-ray patterns verified formation of the β′ form. The calculated activation free energies of nucleation were quite low, but close to the ones published for other fats systems, such as hydrogenated sunflower oil. Only a low supercooling was needed to start crystallization. When isothermal crystallization was studied by NMR, the same behavior was also found for all samples. For low supercooling (crystallization temperatures above 25°C), curves had sigmoidal shapes with a period of induction of crystallization at the beginning. For high supercooling (temperature below 25°C), no induction times were observed as crystallization occurred rapidly. An intermediate plateau in SFC was clearly visible in all curves. The step in this plateau decreased steadily both in rate and height as T_c was increased. The curves were interpreted with the Avrami kinetic model, and parameters K_n and n were calculated. In all cases, the best fit was obtained by setting n to 3. K_n was, on average, 10 times lower above 25°C.     

氢化棉籽油等温结晶动力学的研究

用脉冲核磁共振(PNMR)法测定了两种氢化条件下氢化棉籽油的固体脂肪含量(SFC)。根据不同温度下固体脂肪含量随时间的变化绘制等温结晶曲线。等温结晶曲线有两种:双曲线和反曲线。当过冷却度高时,结晶曲线为双曲线;当过冷却度低时,结晶曲线为反曲线。用Avrami方程进行氢化棉籽油的等温结晶动力学分析,结果表明:过冷却度与晶体的成核和生长方式有显著相关性。当过冷却度高时,结晶常数较小,晶体成核和生长速率快;当过冷却度低时,结晶常数较大,晶体成核和生长速率慢。研究氢化棉籽油的结晶行为对人造奶油、起酥油和可可脂替代品基料油的选择有一定的指导意义。     

Rates of Crystallization of Dried Lactose-sucrose Mixtures

The isothermal crystallization kinetics of glassy lactose/sucrose mixtures were studied at several storage temperatures (close to T_g and T_m). The kinetic parameters implicit in the Avrami equation were determined. Activation energies for transport (E_D) and surface nucleation (W*) were also found and correlated to the molar composition of the lactose/sucrose mixtures. A monotonic increase in the half crystallization time (t_1/z), Avrami index (n), % crystallization per day, activation energy for transport (E_D) and surface nucleation energy (W*) and a decrease in the crystallization velocity constants (K) were related to the increase in the lactose content of lactose/sucrose mixtures.     

几种乳化剂对核桃炼乳的乳化效果研究

针对核桃炼乳加工贮藏过程中易分层的问题,研究了单甘酯(GMS)、蔗糖酯(SE)、Span60、Tween60等乳化剂对核桃炼乳的乳化效果。得到了适宜的HLB值及适宜的复合乳化剂配方。研究结果表明乳化剂的HLB值不同,乳化效果不同。多种乳化剂复合后的乳化效果优于单一乳化剂。对核桃炼乳,适宜的HLB为8.1,适宜的复合乳化剂配方为:20%单甘酯+30%蔗糖酯+33%Span60+17%Tween60。用量为0.4%。     

Honey diastase activity modified by heating

Diastase activity is a honey quality parameter used to determine if honey has been extensively heated during processing. Honey heating effect on the diastase activity was studied in two steps. Heating was carried out in the transient heating step, with final temperatures between 60 and 100 °C and 14 s elapsed time, and in the isothermal heating step, in which temperature was held between 60 and 100 °C at heating times between 120 to 1200 s. Six honey samples with initial diastase activity between 25.8 and 11.2 Schade units were tested. During the transient heating, it was observed a decrease in the diastase activity related to an increase in temperature in all assays. The activity becomes zero at 100 °C for both transient and isothermal heating. During isothermal heating, all samples showed a decrease of the diastase activity at short heating times. However, an activity recovery occurs in medium temperature treatments at longer times. The initial activity value, corresponding to the control sample, was not achieved in any case. This changing behaviour makes diastase activity an uncertain parameter to determine if honey has been submitted to heating.     

STABILITY OF AQUEOUS EMULSIONS OF THE ESSENTIAL OIL OF HOPS

Hop oil emulsions prepared from different varieties of hops have been found to exhibit enhanced physical stability on the addition of blends of the emulsifiers Span 20/Tween 80 or Span 60/Tween 60. Examination of the particle size and volume distributions of an emulsion by use of a Coulter Counter was found to be an excellent method of monitoring its stability. An indication as to the relative efficiency of emulsifiers can be obtained from Coulter Counter measurements on hop oil emulsions after storage for 4 days. The use of an ultracentrifuge provies a rapid means of testing emulsion stability and hence the effectiveness of emulsion stabilizers.     

Effect of Span 60 on the Microstructure,Crystallization Kinetics,and Mechanical Properties of Stearic Acid Oleogels: An In‐Depth Analysis

Modulation of crystallization of stearic acid and its derivatives is important for tuning the properties of stearate oleogels. The present study delineates the crystallization of stearic acid in stearate oleogels in the presence of Span 60. Microarchitecture analysis revealed that stearic acid crystals in the oleogels changed its shape from plate‐like structure to a branched architecture in the presence of Span 60. Consequently, a significant variation in the mobility of the solute molecules inside the oleogel (Fluorescence recovery after photobleaching studies, FRAP analysis) was observed. Thermal analysis (gelation kinetics and DSC) revealed shortening of nucleation induction time and secondary crystallization with an increase in the Span 60 concentration. Furthermore, isosolid diagram suggested better physical stability of the formulations at higher proportions of Span 60. XRD analysis indicated that there was a decrease in the crystal size and the crystallinity of the stearic acid crystals with an increase in Span 60 concentration in the Span 60 containing oleogels. However, crystal growth orientation was unidirectional and found unaltered with Span 60 concentration (Avarmi analysis using DSC data). The mechanical study indicated a composition‐dependent variation in the viscoelastic properties (instantaneous [τ₁], intermediate [τ₂], and delayed [τ₃] relaxation times) of the formulations. In conclusion, Span 60 can be used to alter the kinetics of the crystallization, crystal habit and crystal structure of stearic acid. This study provides a number of clues that could be used further for developing oleogel based formulation.     

Ultrasonic monitoring of lard crystallization during storage

This work addresses the use of ultrasonics as a non-destructive technique with which to monitor lard crystallization during cooling and storage. The ultrasonic velocity was measured during both the isothermal crystallization of lard (at 0, 3, 5, 7, 10 and 20 °C) and during the non-isothermal crystallization. In addition, lard crystallization was also studied through Differential Scanning Calorimetry (DSC) and instrumental texture analysis (penetration tests). The measurement of the ultrasonic velocity allowed the bulk crystallization to be detected. The evolution of the ultrasonic velocity and the textural measurements during isothermal crystallization showed two steep increases, which may be explained by the two fractions of triglycerides found in DSC thermograms. At 7, 10 and 20 °C the second fraction did not crystallize within the first 11 days of storage. A two-step crystallization model based on the Avrami model was used to properly describe (% var > 99.9 and RMSE < 1.99 m s^− 1) the relationship between the ultrasonic velocity and the isothermal crystallization time. In addition, a model was developed to estimate the percentage of solid fat content during isothermal crystallization. Therefore, it may be pointed out that ultrasonic techniques could be useful to monitor the crystallization pattern of complex fats during long periods of storage.     

Ultrasound-assisted liquefaction of rosemary honey: Influence on rheology and crystal content

Crystallization of honey is a common process of the honey industry. Liquid honey is preferred by most of the consumers and by food companies for ease of handling. A better method compared to expensive and time-consuming heating is desirable to accelerate the liquefaction and retard the crystallization process in honey. In this work, samples of crystallized honey were liquefied by an ultrasonic bath of 40 kHz at temperatures of 40-60 °C for 20, 40 and 60 min. Then, the rheological properties and crystal content were analyzed and compared to only heat-treated samples. Results show that an ultrasound treatment speeds up the liquefaction of honey especially at temperatures below 50 °C. Lower temperatures preserve the honey’s quality and save the energy consumption. In addition, ultrasound-treated samples are clearer and more transparent than only heat-treated honey samples. The amount and size of the crystals were also smallest in the ultrasound treated samples.     

Dynamic mathematical model of the crystallization kinetics of fats

A new model able to describe the kinetics of isothermal crystallization is presented: it is a model written in the form of a differential equation allowing use under dynamic temperature variations. It describes the crystallization process as if it is a reversible reaction with a first order forward reaction and a reverse reaction of order n. The model has the advantage of having an analytical solution under isothermal conditions that facilitates parameter estimation. The quality of this model was compared with the more traditional Avrami (with and without induction time) and Gompertz models using different model selection criteria. To show the universality of the model, different fat samples, different crystallization temperatures and different measuring techniques were used for model evaluation. The new model was selected as the best for the majority of the samples and this independent of the model selection criterion used.     

分提棕榈油性质及其等温结晶过程研究

对比分析熔点为44℃(A)、24℃(B)两种分提棕榈油甘三酯组成、固脂含量、等温结晶特性及等温结晶动力学规律。结果表明：甘三酯的组成对于两者的结晶性能具有很大影响。在等温结晶过程中,样品A能够较快速达到结晶终点。在各等温条件下,A的Avrami指数n与B相差不大,说明两者基于过冷状态下的结晶机理相同。     

导电炭黑/聚酯复合材料的等温结晶行为

通过广角X射线衍射仪、差示扫描量热仪测试导电炭黑/聚酯（CB/PET）复合材料的结晶行为,应用Avrami方程分析其等温结晶动力学。结果表明：CB/PET比纯PET具有更完善的结晶和更高的结晶度;随着结晶温度的升高以及CB质量分数的增加,CB/PET的结晶速率明显提高;与纯PET相比,CB/PET的结晶速率、晶粒尺寸和结晶度增加;Avrami参数（n,K,t1/2）对结晶温度非常敏感,n、K随着温度的升高而增加,而t1/2随温度的升高而减小,在相同的结晶温度下,n、t1/2都随着CB质量分数的增加而减小。     

Crystallization kinetics of palm oil in blends with palm-based diacylglycerol

Crystallization kinetics of palm oil (PO) in the presence of different concentrations (2, 5, 10, 30 and, 50% w/w) of palm-based diacylglycerol (PB-DAG) were investigated over different ranges of crystallization temperatures. Addition of 30 and 50% (w/w) of PB-DAG (high concentrations) increased significantly (P < 0.05) the melting point and crystallization onset while addition of 2 and 5% PB-DAG did not have significant (P > 0.05) effect. PO and PO blends with 2 and 5% of PB-DAG showed crystal transformation at crystallization temperatures (T_Cr) of 26, 26, 26.5 °C, respectively as reflected in corresponding changes of the Avrami parameters at below and above these T_Cr. This was especially evident for the blends containing 2 and 5% of PB-DAG. Individual comparison of induction time (T_i), Avrami exponent (n), Avrami constant (k) and half-time of crystallization (t_1/2) of blends classified under various supercooling ranges based on the supercooling closeness (± 0.1 °C), showed that addition of 5% of PB-DAG in most of the supercooling ranges significantly (P < 0.05) reduced nucleation rate as well as crystal growth velocity of PO. This was reflected in the significantly (P < 0.05) higher T_i and t_1/2 and lower k. Although the presence of 2% of PB-DAG was found to have inhibitory effect on PO crystallization, this effect was not significant (P > 0.05). Mode of crystal growth attributed to n was changed significantly only in presence of 5% of PB-DAG. Furthermore, presence of 10% PB-DAG showed ??'-stabilizing effect on PO. On the other hand, high concentrations of PB-DAG were found to significantly (P < 0.05) reduce T_i as well as t_1/2 and also increase k suggesting their promoting effects on nucleation and crystallization rate of PO even with the close supercoolings. In addition, they changed crystal growth mode of PO. Amongst the different concentrations of PB-DAG investigated, blend containing 50% of PB-DAG as compared to PO, not only, have healthier benefits but also, may have greater potential applications in plastic fat products due to its unique physical properties.     

复配乳化剂HLB值对稀奶油脂肪聚结及结晶的影响

将单,双甘油脂肪酸酯与蔗糖酯按一定比例复配成不同亲水亲油平衡（hydrophile lipophilic balance,HLB）值的乳化剂,研究复配乳化剂HLB值对稀奶油脂肪聚结及结晶影响,并对其乳液性质及打发性质进行表征。结果表明,随着复配乳化剂HLB值的增大,乳液粒径增大且表观黏度升高进而使搅打时间延长;热力学及Avrami等温结晶动力学结果表明,复配乳化剂HLB值为10时,高熔点乳脂熔融温度改善显著,并且结晶速率最快;HLB值为8～10时打发性较好,乳清泄漏率较低,涂抹性较佳。因此,复配乳化剂HLB值应控制在8～10,此时更适用于高品质裱花稀奶油的工业生产。     

Process stability of Capsicum annuum pectin methylesterase in model systems, pepper puree and intact pepper tissue

Process stability studies towards temperature and/or pressure on pepper pectin methylesterase (PME) were carried out in different systems (purified form, crude extract, pepper pieces and puree) at pH 5.6. Within the temperature range studied (22–80 °C, 5 min), pepper PME in pure form and crude extract was gradually inactivated showing a biphasic inactivation behaviour, indicating the presence of isoenzymes of different thermostability. Pepper samples heated for 15 min showed a maximum of residual PME activity around 55 °C. Isothermal inactivation of pepper PME in purified form and crude extract at pH 5.6 could be described by a biphasic inactivation model for the temperature range studied (62–76 °C). A stable behaviour towards high-pressure/temperature treatments (400–800 MPa/25–60 °C) was observed for crude extract and purified pepper PME. PME in pepper puree samples revealed to be very pressure stable. Mild temperatures combined with pressure treatments seem to increase the extractability from PME in pepper tissue, probably due to the effect on the cell structure.     

Role of emulsifier layer,antioxidants and radical initiators in the oxidation of olive oil-in-water emulsions

Lipid oxidation in oil-in-water (O/W) emulsions is largely affected by the properties of the interfacial layer surrounding the oil droplets. In this work, the effect of the emulsifier layer structure, presence of both hydrophilic and lipophilic antioxidants and radical initiators on the development of lipid oxidation in olive oil-in-water emulsions was investigated. The olive oil-in-water emulsion is a suitable model of low fat food emulsions. The rationale of the work was to study the role of the interfacial layer when both the antioxidants and the radical initiators came from the two different emulsion compartments. Emulsions were prepared by using food grade emulsifiers of the Tween series (polyoxyethylene sorbitan esters) in the water phase and Span 80 (sorbitan monoleate) in the oil phase. The properties of the interfacial layer were changed by using Tween 20, Tween 60, Tween 80, which have different hydrophobic tails. These systems were oxidized by means of both hydrophilic (AAPH (2,2′-azobis,2-methyl-propanimidamide dihydrochloride), AIPH (2,2′-azobis[2-(2-imidazolin-2-yl) propane] dihydrochloride) and lipophilic (AMVN (2,2′-azobis(2,4-dimethylvaleronitrile)) radical initiators at 40 °C. A continuous fluorescent method based on the front face technique allowed us to follow directly the development of oxidation in the whole emulsion. The combination Tween 80/Span 80 produced an interfacial layer more resistant to radical attack. Moreover, a polar paradox was verified also for radical initiators, while the results suggest that the best way to protect emulsions is to use a combination of antioxidants in both phases, to promote a synergy and the regeneration of antioxidants mediated by the interfacial layer.